Packaged Oxidative Dye Compositions, Methids, and Kits

ABSTRACT

A container for storing oxidative dyes that is stable, inexpensive, light weight, free from environmental issues, has good light resistance, and good barrier properties.

This application claims priority from copending PCT/US2009/041667, filed Apr. 24, 2009, which claims priority of provisional application Ser. No. 61/048,592, filed Apr. 29, 2008, now expired, the entire disclosure of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

Marketed oxidative dye compositions (usually stored in a brown glass bottle) with an aqueous oxidizing agent composition (usually stored in a plastic container) present storage problems. The aqueous oxidizing agent composition typically comprises water and an oxidizing agent such as urea peroxide, hydrogen peroxide, calcium peroxide, and the like. The aqueous oxidizing agent composition contains varying levels of hydrogen peroxide, and is generally characterized as 10 volume, 20 volume, and 30 volume, with the higher volume corresponding to a greater concentration of hydrogen peroxide. It is difficult to find thermoplastic containers that are suitable for storing these compositions. Most thermoplastics will leach into the plastic, cause it to corrode, or otherwise compromise storage stability. Accordingly, high density polyethylene (HDPE) is most often used to make bottles in which developer is sold. Such HDPE is an inexpensive, stable material for use in manufacturing containers used to store aqueous oxidizing agent compositions.

More recently, certain grades of PVC (polyvinyl chloride) thermoplastic materials have been used to manufacture containers suitable for storage of oxidative dyes. PVC containers are very light weight, inexpensive, and exhibit adequate barrier properties for storing oxidative dyes. However, due to perceived environmental concerns, PVC is coming under increasing scrutiny.

This invention provides a container for storing oxidative dyes that is stable, inexpensive, light weight, free from environmental issues, has good light resistance, and good barrier properties.

SUMMARY OF THE INVENTION Detailed Description I. The PET Container

A. Container Composition

The container used for storing the oxidative dye composition is made from a copolyester thermoplastic material, preferably polyethylene terephthalate (PET). In general, PET may be synthesized by reacting ethylene glycol with either dimethyl terephthalate (DMT) or terephthalic acid (TPA). Whether DMT or TPA is used to form the intermediate bis-hydroxyethyl terephthalate, the second step in the polymerization process is generally as set forth below:

with the polymer having repeating units as set forth above between brackets. The polymer may have a molecular weight ranging from about 10,000 to 10,000,000 depending on the type of container that is being made from the PET. In general there is a direct correlation between hardness and the degree of polymerization. Generally, molecular weight or intrinsic viscosity has a bearing on the properties of PET. PET used in containers for storing an oxidative dye composition has an intrinsic viscosity range from about 0.50 to about 2.20.

PET Specifications:

Preferred ASTM Test Specification Preferred Range Value Method General Properties Specific gravity 1.0 to 2.0 1.33 D792 Density 1.0 to 1.20 g/cm³ 1.33 g/cm³ ISO 1183, Method D Mechanical Properties Tensile stress @ yield  30 to 100 MPa, or  58 MPa, or D638 7000 to 9000 psi  8400 psi Tensile stress @ break  15 to 75 MPa, or  25 MPa, or D638 2000 to 6000 psi  3600 psi Elongation @ break  100 to 150% 120% D638 Tensile modulus 1500 to 5000 MPa, or 2400 MPa, or D638 2.5 to 5.0 × 10⁵ psi 3.5 × 10⁵ psi Flexural modulus 1000 to 5000 MPa, or 2500 MPa, or D790 2.5 to 5.0 × 10⁵ psi 3.6 × 10⁵ psi Flexural yield strength  25 to 100 MPa, or  84 MPa, or D790 8500 to 15000 psi 12200 psi Rockwell hardness,  90 to 125 112 D785 R scale Optical Properties Haze 0.5 to 1.5% 1.0% D1003 Total transmittance  50 to 125%  84% D1003

The PET may be light amber or brown, uncolored, or opaque. An example of a PET Resin is Eastman EN001, a thermoplastic polyester copolymer modified with 1,4-cyclohexanedimethanol (CHDM).

The PEG container used to store the oxidative dye compositions may be in the form of bottles, jars, packettes, tubes, and the like.

The oxidative dye composition suitable for storing in the PET containers according to the invention may be in aqueous or anhydrous form, but is preferably an aqueous based composition comprising oxidative dyes and water. The oxidative dye composition may be in the form of a liquid, semi-solid, or solid. It may be in the form of an oil-in-water or water-in-oil emulsion. Generally, the amount of water in the composition ranges from about 0.5-98% water, preferably from about 1 to 95%, more preferably from about 5 to 80% by weight of the total oxidative dye composition. The oxidative dyes contain dye compounds and, optionally other ingredients as further described herein.

The oxidative dye composition may contain one or more primary intermediates, which are dyestuff components. Suggested ranges of primary intermediates are 0.0001-6%, preferably 0.0005-5.5%, more preferably 0.001-5% by weight of the total composition. Such primary intermediates include ortho or para substituted aminophenols or phenylenediamines, such as para-phenylenediamines of the formula:

wherein R₁ and R₂ are each independently hydrogen, C₁₋₆ alkyl, or C₁₋₆ alkyl substituted with one or more hydroxy, methoxy, methylsulphonylamino, aminocarbonyl, furfuryl, unsubstituted phenyl, or amino substituted phenyl groups; R₃, R₄, R₅, and R₆ are each independently hydrogen, C₁₋₆ alkyl, C₁₋₆ alkoxy, halogen, or C₁₋₆ alkyl substituted with one or more hydroxy or amino groups.

Specific examples of suitable primary intermediates include para-phenylened iamine, 2-methyl-1,4-diaminobenzene, 2,6-dimethyl-1,4-d iaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3-dimethyl-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 2-methoxy-1,4-diaminobenzene, 1-phenylamino-4-aminobenzene, 1-dimethylamino-4-aminobenzene, 1-diethylamino-4-aminobenzene, 1-bis(beta-hydroxyethyl)amino-4-aminobenzene, 1-methoxyethylamino-4-aminobenzene, 2-hydroxymethyl-1,4-diaminobenzene, 2-hydroxyethyl-1,4-diaminobenzene, 2-isopropyl-1,4-diaminobenzene, 1-hydroxypropylamino-4-aminobenzene, 2,6-dimethyl-3-methoxy-1,4-diaminobenzene, 1-amino-4-hydroxybenzene, and derivatives thereof, and acid or basic salts thereof.

Preferred primary intermediates are p-phenylenediamine, p-aminophenol, o-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2,5-diaminotoluene, their salts and mixtures thereof.

The oxidative dye composition contains from about 0.0001-10%, of one or more color couplers which are dyestuff components. Suitable color couplers include, for example, those having the general formula:

wherein R₁ is unsubstituted hydroxy or amino, or hydroxy or amino substituted with one or more C₁₋₆ hydroxyalkyl groups, R₃ and R₅ are each independently hydrogen, hydroxy, amino, or amino substituted with C₁₋₆ alkyl, C₁₋₆ alkoxy, or C₁₋₆ hydroxyalkyl group; and R₂, R₄, and R₆ are each independently hydrogen, C₁₋₆ alkoxy, C₁₋₆ hydroxyalkyl, or C₁₋₆ alkyl, or R₃ and R₄ together may form a methylenedioxy or ethylenedioxy group. Examples of such compounds include meta-derivatives such as phenols, catechol, meta-aminophenols, meta-phenylenediamines, and the like, which may be unsubstituted, or substituted on the amino group or benzene ring with alkyl, hydroxyalkyl, alkylamino groups, and the like. Suitable couplers include m-aminophenol, 2,4-diaminotoluene, 4-amino, 2-hydroxytoluene, phenyl methyl pyrazolone, 3,4-methylenedioxyphenol, 3,4-methylenedioxy-1-[(beta-hydroxyethyl)amino]benzene, 1-methoxy-2-amino-4-[(beta-hydroxyethyl)amino]benzene, 1-hydroxy-3-(dimethylamino)benzene, 6-methyl-1-hydroxy-3[(beta-hydroxyethyl)amino]benzene, 2,4-dichloro-1-hydroxy-3-aminobenzene, 1-hydroxy-3-(diethylamino)benzene, 1-hydroxy-2-methyl-3-aminobenzene, 2-chloro-6-methyl-1-hydroxy-3-aminobenzene, 1,3-diaminobenzene, 6-methoxy-1,3-diaminobenzene, 6-hydroxyethoxy-1,3-diaminobenzene, 6-methoxy-5-ethyl-1,3-diaminobenzene, 6-ethoxy-1,3-diaminobenzene, 1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene, 6-methoxy-1-amino-3-[(beta-hydroxyethyl)amino]-benzene, 6-(beta-aminoethoxy)-1,3-diaminobenzene, 6-(beta-hydroxyethoxy)-1-amino-3-(methylamino)benzene, 6-carboxymethoxy-1,3-diaminobenzene, 6-ethoxy-1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 6-hydroxyethyl-1,3-diaminobenzene, 1-hydroxy-2-isopropyl-5-methylbenzene, 1,3-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene, 5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-amino-benzene, 1-hydroxy-3-(carbamoylmethylamino)benzene, 6-hydroxybenzomorpholine, 4-methyl-2,6-dihydroxypyridine, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 6-aminobenzomorpholine, 1-phenyl-3-methyl-5-pyrazolone, 1-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 5-amino-2-methyl phenol, 4-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindole, 6-hydroxyindoline, 2,4-diamionphenoxyethanol, and mixtures thereof.

Preferred couplers include resorcinol, 1-naphthol, 2-methylresorcinol, 4-amino-2-hydroxy toluene, m-aminophenol, 2,4-diaminophenoxyethanol, phenyl methyl pyrazolone, their salts, or mixtures.

The oxidative dye composition may optionally contain one or more alkalizing agents preferably in a range of about 1-5% based on the total weight of the dye mixture. The term “alkalizing agent” means an ingredient that is capable of imparting alkalinity (e.g. a pH of greater than 7) to the dye mixture. Suitable alkalizing agents include ammonium hydroxide, metal hydroxides, alkanolamines, sodium silicate, metal carbonates, sodium metasilicate, and mixtures thereof. Suitable metal hydroxides and carbonates include alkali metal and alkaline earth metal hydroxides or carbonates. Examples of such metal hydroxides include sodium, potassium, lithium, calcium, magnesium and so on. A particularly preferred alkaline earth metal hydroxide is sodium hydroxide. Suitable alkanolamines include mono-, di-, and trialkanolamines such as monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), 2-aminobutanol, aminoethyl propanediol, aminomethyl propanediol, bis-hydroxyethyl tromethamine, diethanolamine, diethyl ethanolamine, diisopropanolamine, dimethylamino methylpropanol, dimethyl MEA, isopropanolamine, methylethanolamine, mixed isopropanolamines, triisopropanolamine, tromethamine, and mixtures thereof. A particularly preferred alkanolamine is MEA.

The oxidative dye composition may contain one or more fatty acids, and if so suggested ranges are about 0.001-15% by weight of the total composition. If fatty acids are present they may react with the alkalizing agent to form soap in situ, which provides a more shampoo-like character to the aqueous hair color composition once it is applied to hair. Such fatty acids are of the general formula RCOOH wherein R is a straight or branched chain, saturated or unsaturated C₆₋₃₀ alkyl. Examples of suitable fatty acids include oleic acid, stearic acid, myristic acid, linoleic acid, and so on. Particularly preferred is oleic acid.

The oxidative dye composition may also optionally contain one or more conditioners that exert a conditioning effect on hair. A variety of conditioners are suitable including cationic polymers, oily conditioning agents, fatty alcohols, proteins, and so on. A combined total weight of conditioners ranges from about 0.1-25%, by weight of the total composition.

A variety of cationic polymers are suitable such as quaternary derivatives of cellulose ethers or guar derivatives, copolymers of vinylpyrrolidone, polymers of dimethyldiallyl ammonium chloride, acrylic or methacrylic polymers, quaternary ammonium polymers, and the like.

Also suitable are a variety of oily materials that provide good conditioning effect to hair. Suitable oils are liquid at room temperature and may comprise esters, hydrocarbons, and the like. Preferably the composition comprises 0.001-20%, more preferably 0.005-15%, most preferably 0.01-10% by weight of the total composition of such oils. Particularly preferred oily conditioning agents are oils extracted from vegetable sources, specifically meadowfoam seed oil.

Also suitable as conditioning agents are one or more silicones. Suitable silicone hair conditioning agents include volatile or nonvolatile nonionic silicone fluids, silicone resins, and silicone semi-solids or solids.

The oxidative dye composition of the invention may also optionally comprise one or more surfactants that assist in maintaining the composition in the preferred emulsion form and aid in the foaming capability of the composition. Suitable surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, and the like.

Preferably the dye composition contains one or more thickening agents that increase the viscosity of the composition such that when it is applied to hair it doesn't run. The amount of thickening agent if present is about 0.001-5%, by weight of the total composition.

It may be desirable to include one or more solvents in the dye composition. Such solvents assist in solubilizing the primary intermediate dyestuff and coupler dyestuff components, in addition to the other ingredients in the composition. The solvent is preferably present at about 0.01-10% by weight of the total composition.

The dye mixture may contain one or more chelating agents that are capable of chelating the metal ions found in water. If water contains too many extraneous metal ions they can interfere with the coloration process. Preferred ranges of chelating agent are 0.001-5%.

The dye mixture may also contain one or more antioxidants, preservatives fragarences, vitamins and other ingredients.

While the invention has been described in connection with one embodiment, it is not intended to limit the scope of the invention to the particular form set forth but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. 

We claim:
 1. A packaged oxidative hair dye composition comprising an oxidative dye stored in a container comprised of PET having one or more of the following specifications: Preferred ASTM Test Specification Preferred Range Value Method General Properties Specific gravity 1.0 to 2.0 1.33 D792 Density 1.0 to 1.20 g/cm³ 1.33 g/cm³ ISO 1183, Method D Mechanical Properties Tensile stress @ yield  30 to 100 MPa, or  58 MPa, or D638 7000 to 9000 psi  8400 psi Tensile stress @ break  15 to 75 MPa, or  25 MPa, or D638 2000 to 6000 psi  3600 psi Elongation @ break  100 to 150% 120% D638 Tensile modulus 1500 to 5000 MPa, or 2400 MPa, or D638 2.5 to 5.0 × 10⁵ psi 3.5 × 10⁵ psi Flexural modulus 1000 to 5000 MPa, or 2500 MPa, or D790 2.5 to 5.0 × 10⁵ psi 3.6 × 10⁵ psi Flexural yield strength  25 to 100 MPa, or  84 MPa, or D790 8500 to 15000 psi 12200 psi Rockwell hardness,  90 to 125 112 D785 R scale Optical Properties Haze 0.5 to 1.5% 1.0% D1003 Total transmittance  50 to 125%  84% D1003


2. An oxidative hair color kit comprising one receptacle containing a developer and one receptacle containing an oxidative dye composition, wherein the receptacle containing the oxidative dye composition is made from PET having one or more of the following specifications: Preferred ASTM Test Specification Preferred Range Value Method General Properties Specific gravity 1.0 to 2.0 1.33 D792 Density 1.0 to 1.20 g/cm³ 1.33 g/cm³ ISO 1183, Method D Mechanical Properties Tensile stress @ yield  30 to 100 MPa, or  58 MPa, or D638 7000 to 9000 psi  8400 psi Tensile stress @ break  15 to 75 MPa, or  25 MPa, or D638 2000 to 6000 psi  3600 psi Elongation @ break  100 to 150% 120% D638 Tensile modulus 1500 to 5000 MPa, or 2400 MPa, or D638 2.5 to 5.0 × 10⁵ psi 3.5 × 10⁵ psi Flexural modulus 1000 to 5000 MPa, or 2500 MPa, or D790 2.5 to 5.0 × 10⁵ psi 3.6 × 10⁵ psi Flexural yield strength  25 to 100 MPa, or  84 MPa, or D790 8500 to 15000 psi 12200 psi Rockwell hardness,  90 to 125 112 D785 R scale Optical Properties Haze 0.5 to 1.5% 1.0% D1003 Total transmittance  50 to 125%  84% D1003


3. A method for storing an oxidative dye composition over time in a container comprised of PET having one or more of the following specifications: Preferred ASTM Test Specification Preferred Range Value Method General Properties Specific gravity 1.0 to 2.0 1.33 D792 Density 1.0 to 1.20 g/cm³ 1.33 g/cm³ ISO 1183, Method D Mechanical Properties Tensile stress @ yield  30 to 100 MPa, or  58 MPa, or D638 7000 to 9000 psi  8400 psi Tensile stress @ break  15 to 75 MPa, or  25 MPa, or D638 2000 to 6000 psi  3600 psi Elongation @ break  100 to 150% 120% D638 Tensile modulus 1500 to 5000 MPa, or 2400 MPa, or D638 2.5 to 5.0 × 10⁵ psi 3.5 × 10⁵ psi Flexural modulus 1000 to 5000 MPa, or 2500 MPa, or D790 2.5 to 5.0 × 10⁵ psi 3.6 × 10⁵ psi Flexural yield strength  25 to 100 MPa, or  84 MPa, or D790 8500 to 15000 psi 12200 psi Rockwell hardness,  90 to 125 112 D785 R scale Optical Properties Haze 0.5 to 1.5% 1.0% D1003 Total transmittance  50 to 125%  84% D1003 